Infrared spectroscopy

(Spectrum Analysis)
 IR Absorption Range
• The graph shows the regions of the spectrum where
the following types of bonds normally absorb.
 Frequencies calculation

• υ = Frequency (cm-1)
• c = velocity of light (3 x 1010 cm sec-1)
• K = constant (dynes cm-1)
• μ=
 Frequencies calculation
Single = 5 x 105
Double = 10 x 105
Triple = 15 x 105

4.12

m = atomic mass
 Predict C=C freq?
1. Double bond,
K = 10 x 105
2. μ
C, 12; (12x12)/(12+12) = 6

= 1682 cm-1

Experimental = 1650 cm-1

 CLASSIFICATION OF IR BANDS
IR bands can be classified as strong (s), medium (m), or
weak (w), depending on their relative intensities in the
infrared spectrum.
 INFRARED BAND SHAPES
Infrared band shapes come in various forms. Two of the most common are
narrow and broad..

A typical example of a broad band is that displayed by O-H bonds, such as

those found in alcohols and carboxylic acids, as shown below.
 IR Spectrum Analysis
1. Alkanes
2. Akenes
3. Alkynes
4. Benzene
5. Alcohol & Ethers SELF CHECK: Try
6. Aldehyde and Ketone to write the
7. Carboxylic acid functional
8. Ester
groups for 1-12
9. Amine
10. Nitrile
11. Amide
12. Alkyl Halide
 IR SPECTRUM OF ALKANES
Alkanes have no functional groups.
Their IR spectrum displays only C-C and C-H bond vibrations.
Most useful are the C-H bands, which appear around 3000 cm-1.

Since most organic

compounds have these
features, these C-H
vibrations are usually not
noted when interpreting a
routine IR spectrum.
 IR SPECTRUM OF ALKENES
Besides the presence of C-H bonds,
C=C bond stretching vibration at about 1600-1700 cm-1.
=C-H bond stretch, appearing around 3080 cm-1
*
Only alkenes and aromatics show a C-H stretch slightly higher than 3000 cm -1.
Compounds that do not have a C=C bond show C-H stretches only below 3000 cm -1.

Stretching vibrations of
the –C=C–H bond are of
higher frequency (higher
wavenumber) than those
of the –C–C–H bond in
alkanes.
Note how similar they are, except for the bands due to C=C or C=C–H stretches/bends.
 IR SPECTRUM OF ALKYNES

Sharp, weak band at about 2100 cm-1.

Weak is because the triple bond is not very polar.

In some cases, such as in highly symmetrical alkynes, it may not show at

all due to the low polarity of the triple bond associated with those alkynes.

Terminal alkynes, may show a sharp, weak band at about 3300 cm-1
corresponding to the C-H stretch.

Internal alkynes do not have C-H bonds to the sp carbon.

Note the C–H stretch of the C–H bond adjacent to the carbon-carbon triple bond (3324), the
carbon-carbon triple bond stretch (2126), and the C–H bend of the C-H bond adjacent to the
carbon-carbon triple bond (636).
 IR SPECTRUM OF ALKYNES

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR spectra BENZENES

=C—H bond, “unsaturated” “aryl”

(sp2) 3000-3100 cm-1
+ 690-840
mono-substituted + 690-710, 730-770
ortho-disubstituted + 735-770
meta-disubstituted + 690-710, 750-810
para-disubstituted + 810-840

C=C bond 1500, 1600 cm-1

 IR spectra AROMATIC RING
The =C–H stretch in aromatics is observed at 3100-3000 cm-1.
*Slightly higher frequency than is the –C–H stretch in alkanes.
*Only alkenes and aromatics show a C–H stretch slightly higher than 3000 cm -1.
*Compounds that do not have a C=C bond show C–H stretches only below 3000 cm-1.

Aromatic hydrocarbons show absorptions in the regions 1600-1585 cm-1 and 1500-

1400 cm-1 due to carbon-carbon stretching vibrations in the aromatic ring.

Bands in the region 1250-1000 cm-1 are due to C–H in-plane bending, although these
bands are too weak to be observed in most aromatic compounds.

Besides the C–H stretch above 3000 cm-1, two other regions of the infrared spectra of
aromatics distinguish aromatics from organic compounds that do not have an aromatic
ring:
•2000-1665 cm-1 (weak bands known as "overtones")
•900-675 cm-1 (out-of-plane or "oop" bands)
 IR SPECTRUM ALCOHOL
• The O–H stretch of alcohols appears in the region 3500-3200 cm-1 and is a
very intense, broad band.
• The C–O stretch shows up in the region 1260-1050 cm-1..
 IR spectra ALCOHOLS & ETHERS
C—O bond 1000-1300 cm-1
1o ROH 1050
Not necessarily due to C
2 ROH
o
1100 —O bond, but the
absence of absorption in
3o ROH 1150 this region suggests the
absence of C—O bond.
ethers (ROR) 1060-1150
O—H bond 3200-3640 (broad)
alcohol molecules are involved in hydrogen bonding -
different arrangements – resulting in broad absorptions
 IR SPECTRUM OF ALDEHYDES AND KETONES

• Contain the C=O functional group.

• Strong, prominent, stake-shaped band around 1740 - 1720 cm-1 (right in the
middle of the spectrum).
• Due to the highly polar C=O bond.

• O=C–H stretch, generally appears as one or two bands of moderate intensity

in the region 2830-2695 cm-1.

• Because aldehydes also contain a C-H bond to the sp2 carbon of the C=O
bond, they also show a pair of medium strength bands positioned about 2700
and 2800 cm-1. These bands are missing in the spectrum of a ketone because
the sp2 carbon of the ketone lacks the C-H bond.
IR SPECTRUM OF ALDEHYDES

H–C=O stretch 2830-

2695 cm-1

aliphatic aldehydes
1740-1720 cm-1
IR SPECTRUM OF ALDEHYDES

O=C stretch of the alpha,

beta-unsaturated
compound --
benzaldehyde -- is at a
lower wavenumber than
that of the saturated
butyraldehyde.
IR SPECTRUM OF KETONES

C–H
stretches
(around
2991) of
alkyl groups.

The carbonyl stretching

vibration band C=O of
saturated aliphatic
ketones appears at 1715
cm-1.
 IR Spectrum of CARBOXYLIC ACID

• Strong, wide band for the O–H stretch.

• The carboxylic acid O–H stretch appears as a very broad band in
the region 3300-2500 cm-1, centered at about 3000 cm-1.
• Shows a somewhat "messy" absorption pattern in the region
3300-2500 cm-1, with the broad O–H band superimposed on the
sharp C–H stretching bands.
• The reason that the O–H stretch band of carboxylic acids is so
broad is because carboxylic acids usually exist as hydrogen-
bonded dimers.
• The carbonyl stretch C=O of a carboxylic acid appears as an
intense band from 1760-1690 cm-1.
 IR Spectrum of CARBOXYLIC ACID
• O–H stretch from 3300-2500 cm-1
• C=O stretch from 1760-1690 cm-1
• C–O stretch from 1320-1210 cm-1
• O–H bend from 1440-1395 and 950-910 cm-1
 Infrared Absorption Frequencies

Stretching vibrations (carbonyl groups)

Aldehydes, ketones and carboxylic acids
C O
1710-1750
sp2 C-H of aldehydes 2700 and 2800

1710 1710
1710

2700, 2800 Broad, 2500-3500

 IR Spectrum of ESTER
• C=O stretch
– aliphatic from 1750-1735 cm-1
– α, β-unsaturated from 1730-1715 cm-1
• C–O stretch from 1300-1000 cm-1 (two or more bands)
 IR SPECTRA OF AMINES

• N–H stretch 3400-3250 cm-1

*weaker and sharper than those of the alcohol O–H stretches which appear in the same
region.
• 1° amine: two bands from 3400-3300 and 3330-3250 cm-1
• 2° amine: one band from 3350-3310 cm-1 (weak band)
• 3° amine: no bands in this region
• N–H bend (primary amines only) from 1650-1580 cm-1
• C–N stretch (aromatic amines) from 1335-1250 cm -1
• C–N stretch (aliphatic amines) from 1250–1020 cm-1
• N–H wag (primary and secondary amines only) from 910-665 cm -1
How to analyze IR spectra
• If there is an absence of major functional group bands in the region 4000-1300
cm-1 (other than C–H stretches), the compound is probably a strict hydrocarbon.
• Also check the region from 900-650 cm-1. Aromatics, alkyl halides, carboxylic
acids, amines, and amides show moderate or strong absorption bands (bending
vibrations) in this region.
• Not try to assign or interpret every peak in the spectrum. Concentrate on
learning the major bands and recognizing their presence and absence in any
given spectrum.
• Calculate the Degree of Unsaturation

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